Fundamentals of Sour Water Stripping

1
Providing Solutions for Tomorrows Environment 1 Providing Solutions for Tomorrows Environment
Fundamentals of Fundamentals of
Sour Water Stripping Sour Water Stripping
Presented at the
Brimstone Sulfur Symposia
V il C l d S t b 2008 Vail, Colorado, September 2008
David K. Stevens
President & CEO
Alan Mosher
Director of Engineering
2 Providing Solutions for Tomorrows Environment
President & CEO Director of Engineering
2
Outline
Sources and Characteristics of Sour Water
Sour Gas Processing
Refining Processes
l l Claus Tail Gas Treating
Gasification and Similar Processes Gasification and Similar Processes
Processing SWS Offgas in SRU/TGUs Processing SWS Offgas in SRU/TGUs
Alternatives Strategies for Sour Water and Alternatives Strategies for Sour Water and
Sour Gas
Providing Solutions for Tomorrows Environment 3
Sour Gas
Sources and Characteristics of
Sour Water
Sour Gas Processing
Oil Refining
Gasification and Other Thermal Process
Claus Tail Gas Units
3
Sour Gas Processing
Sources of Sour Water
Wellhead Facilities
Dry or Wet Pipeline
Plants
Inlet Separators
Li id KO D Liquid KO Drums
Dehydration Unit Dehydration Unit
Claus Plant
Compressor Aftercoolers
Sour Gas Processing
Sources of Sour Water (cont.)
Plants (cont.)
Dehydration Processes
Glycol Regen Condensate
Solid Bed Absorbent Dehydrator Regen Solid Bed Absorbent Dehydrator Regen
Gas Treating Units Reflux Purge g g
Tail Gas Units Quench Water
4
Sour Gas Processing Characteristics
Two Types of Sour Water
Produced Water
Water that originates in the reservoir and flows up the
tubing with the gas tubing with the gas
Condensed Water
Salt-free Water that condenses from the gas after the
gas has left the producing reservoir gas has left the producing reservoir
Produced Water Characteristics
Originates in Reservoir
Generally Removed in Inlet Separator
H
2
S and CO
2
Salt-Bearing
Anions Cations
Chl id P t i Chlorides Potassium
Bromides Sodium
Sulfates Magnesium
5
Produced Water Characteristics (cont.)
Hydrocarbons
Methanol/Hydrate Inhibitors
Corrosion Inhibitors
Hydrocarbons
Produced Water Processing
Injection Well with Filtration
Local
Remote (Trucked)
Stripping
St I j ti St R b il Steam Injection or Steam Reboiler
Gas Avoids Salting Out Potential Gas Avoids Salting Out Potential
6
Produced Water Processing (cont.)
Offgas Disposal
Flare
Low Tonnage Sulfur Recovery
l Recompression to Pipeline
Evaporation Ponds Evaporation Ponds
Salt Presence Salt Presence
Condensed Water Characteristics
Condensed After Gas has Left Reservoir
Salt Free
H
2
S and CO
2
Glycols H
2
S and CO
2
Hydrocarbons
G yco s
Methanol
Iron Sulfides
Other Hydrate Inhibitors
Amines
Corrosion Inhibitors
7
Condensed Water Processing
Stripping pp g
Steam Injection or Steam Reboiler
Gas
Disposal of Offgas
Fl Flare
Claus Plant Claus Plant
Integrate with Tail Gas Quench teg ate t a Gas Que c
Condensed Water Processing (cont.)
Disposal of Stripped Sour Water p pp
Injection Well
Evaporation Pond
Upgrade to BFW
8
Some Approaches to Sour Water
Stripping in Sour Gas Processing Plants
Integrate a Sour Water Stripper with a Tail Gas g pp
Quench System
Re-use of Tail Gas Quench Water as Boiler Feed
WWater
Integrated Sour Water Stripper with Tail Gas Quench g pp Q
16
9
Reuse of Quench Water for BFW Q
17
Oil Refining Sources of Sour Water
Desalters
/ Crude/Vacuum Units
H d Hydrotreaters
FCC FCCs
Thermal Cracking Thermal Cracking
Hydrocracking Hydrocracking
Amine Treating Amine Treating
10
Oil Refining General Trends
Higher Sulfur and Nitrogen Content Crudes
Deeper Levels of Hydroprocessing
Generate Higher Levels of Sour Water
General Characteristics of
Refinery Sour Water
Typical Concentrations
H
2
S 300 to 12,000 ppm (wt)
NH 100 8 000 ( ) NH
3
100 to 8,000 ppm (wt)
Molar Ratio NH :H S Molar Ratio NH
3
:H
2
S
Between 1 0 and 2 0 Between 1.0 and 2.0
Typical 1.1 to 1.4 yp
Typical pH between 8 and 10
Sour Water pH dictates NH
3
:H
2
S Ratio
11
Refinery Sour Water
Range of Potential Contaminates
Phenol Organic Acids Hydrocarbon
Cyanide Caustic Chloride
Selenium Mineral Acids Hardness Selenium Mineral Acids Hardness
How the Bad Actors Behave
Acidic Anions: Chlorides Sulfates Formates Acidic Anions: Chlorides, Sulfates, Formates
Depress pH p p
Tie-up Ammonium Ion
Alkali Cations: Sodium, Potassium
Raise pH Raise pH
Tie-up Sulfide Ion p
Phenols Not readily strippable
Cyanide Corrosive; use of polysulfides to form
thi t thiocyanate
Naphthenic and Cresylic Acids
Naphthenic and Cresylic Acids
12
How the Bad Actors Behave (cont.)
Heavier Hydrocarbons Multiple problems; Heavier Hydrocarbons Multiple problems;
Can polymerize Can polymerize
Carbon Dioxide Lower pH and tie-up
Ammonia
C l i C i it t h d i Calcium Can precipitate as hardness in
stripper stripper
Oxygen Egress can form acid which fix yg g
Ammonia
Amine Can tie-up Ammonia
Selenium Can precipitate and foul stripper
Selenium Can precipitate and foul stripper
The Problem with Phenols
Phenols are not removed due to solubility
h t i ti t t ffi i i characteristics not tray efficiencies
Phenolic Bearing Units (With Other Phenolic Bearing Units (With Other
Contaminates such as Cyanides and Colloidal Contaminates such as Cyanides and Colloidal
Sulfur)
Cokers
Crude Units
FCC FCCs
ARUs and TGU Purge
ARUs and TGU Purge
13
The Problem with Phenols (cont.)
Non-Phenol Bearing Units g
Hydrotreaters
Desulfurization Units
Chemistry of Refinery Sour Water
Sour Water forms as Water and Hydrocarbon y
are in contact and partition the Hydrogen
Sulfide and Ammonia in accordance with
Henrys Law Henry s Law
The Ammonia and Hydrogen Sulfide dissolved The Ammonia and Hydrogen Sulfide dissolved
in the now Sour Water ionize to the
equilibrium extent according the pH and
temperature
14
Chemistry of Refinery Sour Water (cont.)
Ammonia and Hydrogen Sulfide can only be
stripped if in parent gaseous form i e exerting stripped if in parent gaseous form, i.e. exerting
a partial pressure The iononized components a partial pressure. The iononized components
do not strip
Presence of ions which raise the pH tie-up
Sulfides and aid Ammonia stripping
Conversely presence of ions which lower the
pH tie up the Ammonia and aid Sulfide pH tie-up the Ammonia and aid Sulfide
stripping
stripping
Approach to Sour Water Management
in the Oil Refinery
Stripped Sour Water Specifications
Re-use Strategy
Feed Preparation
Sour Water Stripper
Sour Water Offgas Disposal
15
Stripped Sour Water Specifications
Typical WWTP Influent Requirements
25 ppm Ammonia
10 ppm Hydrogen Sulfide
Lower specs are often observed
W SHA S Benzene Waste NESHAPS
Sour Water Reuse
Recycle All Stripped Sour Water to Desalter or Recycle All Stripped Sour Water to Desalter or
Coker Coker
Segregate Phenolic and Non-Phenolic Sour g g
Water
Recycle Non-Phenolic to
Hydrotreaters/Desulfurizers Hydrotreaters/Desulfurizers
Hydrotreaters cant tolerate Phenols y
SWS only removes 10 to 50 % of Phenol
Recycle Phenolic Sour Water to Desalter were
Oil t t th Ph li C d
Oil extracts the Phenolic Compounds
16
Sour Water Feed Preparation
Inlet Feed Separation and Hydrocarbon Flash
and Skimming
Vent to Safe Location
d Sour Water Feed Surge
3 D St T t 3-Day Storage Target
Oil Skim Oil Skim
Design to Prevent Short Circuit g
Sour Water Stripper Design
Non-Refluxed
Direct Steam Injection or Reboiler
Very High Water Content of Offgas
(70 % l @13 i ) (70+% vol @ 13 psig)
Refluxed Refluxed
Direct SteamInjection or Reboiler Direct Steam Injection or Reboiler
Overhead Condenser or Pump Around p
Conventional Practice (40+% vol @ 13 psig)
17
Conventional Sour Water Stripper
Practice: Oil Refinery
T M i D i Ch i P /C Two Main Design Choices Pros/Cons
Pump Around vs Overhead Condenser Pump Around vs. Overhead Condenser
Direct SteamInjection vs. Reboiler Direct Steam Injection vs. Reboiler
General Trends
Steam to Feed Ratio
Feed Tray Location
Feed Concentration
St C t d N b f T Steam Cost and Number of Trays
Caustic Injection and Chlorides
Caustic Injection and Chlorides
Conventional Overhead Condenser
34
18
Pump Around Condenser p
35
Sour Water Stripper Design Approach
l f Materials of Construction
CS as predominant choice in the da CS was predominant choice in the day
Overhead Line was most often upgraded pg
Current designs upgrade especially as function of
f d feed
Simulation Basis Simulation Basis
Sour Pro/II
GPA Sour Pro/II
OLI El t l t P /II ( ti i j ti t di ) OLI Electrolyte Pro/II (caustic injection studies)
Elusive Phenol Removal Process?
Elusive Phenol Removal Process?
19
(cont.)
Design Basis Issues g
Dont Over Estimate Feed Sourness
Tower Stability and Control Problems
MOC Upgrade Creep
Design Margin Creep Design Margin Creep
(cont.)
Nice to Haves
Cant ha e eno gh h drocarbon skimming Cant have enough hydrocarbon skimming
capability p y
Likewise with surge and storage but be
reasonable
Dual Reboilers Dual Reboilers
Live SteamInjection Live Steam Injection
Some degree of redundancy/overcapacity for
catch-up and addressing the inevitable fouling
episode(s)
episode(s)
20
Sour Water Offgas Disposal
Flare - Back-up and Limited
Fired Heaters
Direct Combustion of SWS Offgas
Separate NH
3
from H
2
S and Burn Ammonia in
Heater Heater
Claus SRUs Claus SRUs
The Most Common Approach pp
And the Most Interesting
Separate Ammonia from
Hydrogen Sulfide
Most common approach in refinery application Most common approach in refinery application
is Chevron WWT is Chevron WWT
Two Column Operation p
Ammonia can be recovered
Aqueous
Anhydrous Anhydrous
Main Concerns Main Concerns
CAPEX (Due to Equipment Count and MOC)
Complexity
Ammonia Sales
Ammonia Sales
21
Chevron WWT Process
41
Sour Water From Claus Tail Gas Treating
Sour Water Produced fromQuench Sour Water Produced from Quench
Claus / Tail Gas Feeds Claus / Tail Gas Feeds
Components Components
H
2
S TOC
NH
3
Thiosulfate
CO Sulfide
Production Characteristics
CO
2
Sulfide
100 LTPD S Generates 10.5 gpm Sour Water
100 STPD Ammonia Generates 40.5 gpm Sour
Water
Water
22
Calculated Effect of Sour Water Stripper Offgas in
Claus SRUs on Quench Water Purge
15
16
m
14
15
u
r
g
e
,

g
p
m
13
W
a
t
e
r

P
u
12
u
e
n
c
h

W
10
11
u
o
u
s

Q
u
9
10
C
o
n
t
i
n
u
8
0 5 10 15 20 25 0 5 10 15 20 25
% NH
3
(vol) in Total Amine Acid Gas plus SWS Offgas
(Constant 100 ETPD)
43
Calculated Effect of Sour Water Stripper Offgas in
Claus SRUs on Quench Water Purge
60
m
50
g
e
,

g
p
m
40
a
t
e
r

P
u
r
g
30
e
n
c
h

W
a
20
o
u
s

Q
u
e
10
C
o
n
t
i
n
u
o
0
C
0
0 5 10 15 20 25
% NH
3
(vol) in Total Amine Acid Gas plus SWS Offgas
44
3
( ) p g
(100 LTPD Amine Acid Gas)
23
Gasification and Other Similar Processes
G d i d f C l Gases derived from Coal
Producer Gas Producer Gas
Water Gases
Coke Oven Gas
By-product of Coal Coking
Coal or Pet Coke Gasification
Syngas for Power
i Ammonia
Synthetic Natural Gas
Synthetic Natural Gas
Sour Water From Gasification
and Other Similar Processes
Ammonia and Cyanides Produced During the
Thermal Processing are present in the coal-
d d derived gas
U t 1 % l A i Up to 1 % vol Ammonia
0 1 to 0 25% vol Hydrogen Cyanide 0.1 to 0.25% vol Hydrogen Cyanide
Processes Available to Remove the Ammonia Processes Available to Remove the Ammonia
directly from the Coal-Derived Gas
24
Sour Water From Gasification
and Other Similar Processes (cont.)
Typical Thermal Processing involves some form
of Water Quench or Scrubber
The Sour Water contains all the Ammonia and
some of the Hydrogen Sulfide fromthe coal derived some of the Hydrogen Sulfide from the coal-derived
gas
Other water soluble components like organic acids
d h l and phenols are present
Some Interesting Processes from the g
Coal Gas Industry Practices & Experience
Direct Ammonia Removal Processes
React with Strong H
2
SO
4
or H
3
PO
4
to Produce
lf h h d Ammonium Sulfate or Ammonium Phosphate and
Acid Gas Acid Gas
Phosam Process to Separate NH
3
and Acid Gases
3
from the Gas Stream
25
Some Interesting Processes from the g
Coal Gas Industry Practices & Experience
Ammonia Processing After Water Scrubbing
and Sour Water Stripping
Catalytic Destruction of NH
3
in Presence of H
2
S
O id ti f NH d H S i Cl Pl t Oxidation of NH
3
and H
2
S in Claus Plant or
Incinerator
Ammonium Sulfate or Ammonium Phosphate p
50
26
Phosam Process
51
Catalytie NH
3
Destruction and Sulfur Recovery y
3
y
52
27
Even More Interesting Processes from
the Coke-Oven Gas Processing Industry
Process for Ammonia Removal and Recovery
from Ammonia Bearing Acid Gas
Processes for Ammonia and Hydrogen Sulfide
R l U i A i Removal Using Ammonia
Ammonia Removal and Recovery o a e o a a d eco e y
54
28
Acid Gas and Ammonia Removal with Ammonia Recovery c d Gas a d o a e o a t o a eco e y
55
Chemistry of Ammonia-Based
Processes for H
2
S and CO
2
Removal
Hydrogen Sulfide
2 NH
3
(g) + H
2
S (g) (NH
4
)
2
S
3
(g)
2
(g) (
4
)
2
NH
3
(g) + H
2
S (g) (NH
4
) HS (aq)
Carbon Dioxide
2 NH
3
(g) + CO
2
(g) + H
2
O (l) (NH
4
)
2
CO
3
(aq)
2 NH
3
(g) + CO
2
(g) NH
4
CO
2
NH
2
(aq)
29
Sour Water Offgas to Claus SRUs
Normally can process up to 2 4% (vol) Normally can process up to 2 4% (vol)
ammonia in Claus SRU without modification to
a conventional straight-through design
Above this level need additional design
considerations: preheat two zone thermal considerations: preheat, two-zone thermal
reactor etc. reactor etc.
Over 25% (vol) ammonia in total feed gases ( ) g
need to address potential NO
x
formation
Sour Water Offgas to Claus SRUs (cont.)
Typically like to see Claus thermal reactor
effluent ammonia content less than 100 ppmv effluent ammonia content less than 100 ppmv
Some reports of Claus thermal reactor effluent p
ammonia up to 500 to 600 ppmv without
difficulty difficulty
Overhead Line Temperature Maintenance Overhead Line Temperature Maintenance
KO Drum KO Drum
Contains No Demister
Multiple Level Devices Multiple Level Devices
Fully Traced and Insulated
30
Instrument Taps
Large (2 or 3 on Vessel)
All Traced All Traced
Diaphragm Seals p g
Steam Outs
O i d V t i T Oversized Venturi Taps
High Level Trip High Level Trip
Isolates Sour Water Offgas Only
Mixing SWS Gas with Amine Acid Gas
l i Salt Formation
Under Deposit Corrosion Under Deposit Corrosion
All Lines No Pocket and Top Entry p y
Minimum Distance After Mix Point
31
Amine Acid Gas Preheater
Process on Tube Side
BEM Axial Flow Configuration to Eliminate Pockets
Si l P t Eli i t P k t Single Pass to Eliminate Pockets
Tube Sheet Material SA-516-70 w/ 0 1875 (min ) Tube Sheet Material SA 516 70 w/ 0.1875 (min.)
347 SS Overlay
Tube Material SA-249-TP 321 SS
All 321 SS M i l S bili d / A l d All 321 SS Materials are Stabilized / Annealed
Tube to Tubesheet Joint is Rolled and Seal Welded
Tube to Tubesheet Joint is Rolled and Seal Welded
Ammonia Salts
Solids Deposition Possibilities
Ammonia Forms a Number Salts That Can
Produce Deposits
Ammonium Hydrosulfide
NH H S NH HS NH
3
+ H
2
S NH
4
-HS
AmmoniumCarbamate Ammonium Carbamate
2NH
3
+ CO
2
NH
4
-CO
2
-NH
2 3 2
4 2 2
Ammonium Bicarbonate
NH
3
+ CO
2
+ H
2
O NH
4
-HCO
3
32
Ammonia Salts
Solids Deposition Possibilities (cont.)
Deposition Temperature Depends on Partial
Pressures of NH
3
, H
2
S, CO
2
and H
2
O
Salts Typically Begin Depositing from 70 - 140F
Best Practice is Stay at Least 45F Hotter than
C l l t d D iti T t Calculated Deposition Temperature
64
33
Theoretical Impact of Processing Sour Water p g
Stripper Offgas on Claus/Tail Gas Unit Capacity
Claus Reaction Claus Reaction
H
2
S + 3/2 O
2
SO
2
+ H
2
O
2 H
2
S + SO
2
3S + H
2
O
3 H
2
S + 3/2 O
2
3S + 2 H
2
O
Ammonia Combustion
3 H
2
S 3/2 O
2
3S 2 H
2
O
2NH
3
+ 3/2O
2
2N
2
+ 3H
2
O
Overall
3/2 lb mole O
2
2 lb mole NH
3
17 lb NH
3
1 lb mole S ST NH
3
2240 lbs S
3 lb mole S 3/2 lb mole O2 1 lb mole NH
3
32 lbs 2000 lb NH3 LT S
65
Calculated Effect of Processing SWS g
Offgas on Claus/Tail Gas Unit Capacity
100 tpd Claus/Tail Gas Unit
Acid Gas (vol %) SWS Offgas (vol %)
87.5% H
2
S
4 5% CO
23.2% H
2
S
33 1% NH 4.5% CO
2
1.9% C
1
33.1% NH
3
41.6% H
2
O 1.9% C
1
6.1% H
2
O
41.6% H
2
O
2.1% C
1
34
Calculated Effect of Processing SWS Offgas on g g
Claus / Tail Gas Capacity at Constant Air Demand
100 100
80 80
N
H
3
e
d
60 60
p
l
u
s

E
T
P
D

u
r

P
r
o
d
u
c
40 40
P
D

S
u
l
f
u
r

p
L
T
P
D

S
u
l
f
u
20 20
L
T
P
0 0
0 5 10 15 20 25
NH3% (vol) in Total Amine Acid Gas plus SWS Offgas
67
NH3% (vol) in Total Amine Acid Gas plus SWS Offgas
Calculated Effect of Processing SWS Offgas on Calculated Effect of Processing SWS Offgas on
Claus / Tail Gas Capacity at Constant Air Demand
50 100
40
90
80
30
70
P
D

N
H
3
D

S
u
l
f
u
r
20
60
E
T
P
L
T
P
D
10
50 50
0 40
0 5 10 15 20 25
% NH3 (vol) in Total Amine Acid Gas plus SWS Offgas
68
% ( ) p g
35
Calculated Impact Analysis Based Only
on Required Air Demand
What About Actual Performance Characteristics?
Simulated Effect of Processing Sour Water g
Stripper Offgas in Claus / Tail Gas Units
6 85
6 80
6.85
6.75
6.80
Kinetic - Split Flow Model
6.70
M
M
S
C
F
D
Kinetic - Straight Thru Model
Models are from Sulsim Version 6.0.
6.65
D
e
m
a
n
d
,
M
Note that Air Demand predicted by
various models differs by < 5%.
6.60
A
i
r

Kinetic - NH3 Burn Model
Ki i Th d i M d l
6.55
Kinetic - Thermodynamic Model
6.50
0 5 10 15 20 25
( l) i l i id l ff
70
36
Simulated Effect of Sour Water Stripper Offgas pp g
in Claus SRUs on Pressure Drop
1200
1100
1000
/
h
r
900
a
t
e
,
l
b
m
o
l
/
Claus Tail Gas velocity increases by ~12% as NH3
content is increased from 0 - 25%.
Pressure drop is proportional to the square of the
l
800
F
l
o
w
r
a
velocity.
Pressure drop is increased by ~25% in SRU. Effect is
less dramatic downstream of Quench Tower.
700
600
700
600
0 5 10 15 20 25
(C t t 100 ETPD)
71
(Constant 100 ETPD)
New Plant Construction
400
350
400
300
350
250
200
T
P
D
S
u
l
f
u
r
150
E
T
100
Amine Acid Gas H2S
50
0
0 5 10 15 20 25
%NH3 (vol) in Total Amine AcidGas plus SWS Offgas
72
37
CAPEX Approximation
Basic 100 tpd Claus/Tail Gas Unit is
US$25MM
Typical Two-Bed Claus
20 24 M i G Li 20 or 24 Main Gas Line
Conventional TGU plus Incinerator Conventional TGU plus Incinerator
CAPEX Approximation (cont.)
Adding Ammonia Processing
5% - 115 ETPD is US$28MM (105 LTPD S & 4 STPD NH3)
15% - 165 ETPD is US$35MM (125 LTPD S & 16 STPD NH3) 15% 165 ETPD is US$35MM (125 LTPD S & 16 STPD NH3)
38
Whats it Worth?
10% Ammonia Feed
Additional US$6MM CAPEX
OPEX?
l $ / Ammonia Nearly US$3MM/Year
20% Ammonia Feed 20% Ammonia Feed
Additional US$19MMCAPEX Additional US$19MM CAPEX
OPEX?
Ammonia Nearly Over US$11MM/Year
Alternative Sour Water Management
Processes
Ammonia Separation from Sour Water
Processes
Chevron WWT Process
US Steel PhosamProcess US Steel Phosam Process
Uses for Recovered Ammonia
Recover as Anhydrous Ammonia
Ammonia Sulfate
AmmoniumThiosulphate Ammonium Thiosulphate
Hydrogen
39
Alternative Sour Water Stripper Offgas
Processes
Di S W S i Off C b i Direct Sour Water Stripper Offgas Combustion
with SO Scrubbing with SO
2
Scrubbing
NO Production? NO
x
Production?
John Zink Noxidizer
SCR SNCR? SCR or SNCR?
SO
2
Scrubbing SO
2
Scrubbing
Cansolv (SO
2
Recycle)
C ti Caustic
Ammonia (Ammonia Sulfate or Ammonia Thiosulphate)
Hydrogen Can be produced from Ammonia
(No Joke)
(No Joke)
Noxidizer with Caustic Scrubber Noxidi er with Caustic Scrubber
78
40
SCR Combustion with SCR and Cansolv Scrubber SCR Combustion with SCR and Cansolv Scrubber
79
Ammonia Thiosulphate Production Ammonia Thiosulphate Production
80
41
Some Reflections on Sour Water
There are many different approaches to
managing sour water most successful, some
h f not with a few mysteries remaining
Some Reflections on Sour Water (cont.)
Wh t i th R fi B k P i t t L k t What is the Refiners Break Point to Look at
Alternatives? Alternatives?
Removing Load fromClaus Options? Removing Load from Claus Options?
Typical Water Cost and Upgrade Complexity to BFW
City / Potable
Well Well
Surface
Sour Water Sour Water
Is Ammonia Recovery a Better Way Re-look at
Economics given Energy Costs and Green
Solutions???
Solutions???

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